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. 2024 Dec 6;89(23):17615-17620.
doi: 10.1021/acs.joc.4c02383. Epub 2024 Nov 17.

Development of a Highly Enantioselective Catalytic Di-π-methane Rearrangement

Samuel B Cahoon  1 , Steven J Chapman  1 , Tahoe A Fiala  1 , Matthew J Genzink  1 , Tehshik P Yoon  1
Affiliations

Development of a Highly Enantioselective Catalytic Di-π-methane Rearrangement

Samuel B Cahoon et al. J Org Chem. .

Abstract

The di-π-methane (DPM) rearrangement is an important organic photorearrangement that converts 1,4-diene-containing compounds to vinyl cyclopropanes, often resulting in extensive, synthetically valuable restructuring of the substrate's carbon framework. We investigated the influence of Lewis and Brønsted acids on the DPM rearrangement of dibenzobarrelenes. These studies have culminated in the identification of a dual chiral Brønsted acid-iridium photosensitizer system that enables the first highly enantioselective catalytic all-carbon DPM rearrangement.

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